Thermoplastically processable aromatic polyether amide

ABSTRACT

Thermoplastically processable aromatic polyether amide 
     Thermoplastically processable aromatic polyether amide of the formula (I) ##STR1## in which the symbols Ar, Ar&#39;, Ar 1 , Ar 2 , R, R&#39;, Y, x, y and z have the following meanings: 
     Ar is a divalent, substituted or unsubstituted, aromatic or heteroaromatic radical or a group 
     
         --Ar*--Q--Ar*-- 
    
      in which 
     Q is a bond or an --O--, --C(CH 3 ) 2 , --CO--, --S--, --SO-- or --SO 2  -- bridge and Ar* is an aromatic radical. The carbonyl groups of the Ar radical are on non-adjacent ring carbon atoms. 
     A is up to three different radicals. 
     Ar&#39; has the meaning given for Ar or is an Ar--Z--Ar group. 
     In this case, Z is a --C(CH 3 ) 2  -- or --O--Ar*--O--bridge. 
     Y is a --C(CH 3 ) 2  --, --SO 2  --, --S-- or a --C(CF 3 ) 2  --bridge and has up to two different meanings in the same polymer. 
     Ar 1  and Ar 2  are identical or different from one another and are each a substituted or unsubstituted para- or meta-arylene radical. The sum of the mole fractions x, y and z is one. The sum of x and z may not be equal to y and x can assume the value zero. In a preferred embodiment, z is greater than x.

BACKGROUND OF THE INVENTION

Thermoplastically processable aromatic polyether amide

The invention relates to thermoplastically processable aromaticpolyether amides laving a high heat distortion point, their preparationvia solution or melt condensation, and their use for the production ofshaped articles, filaments, fibers, films and coatings.

Aromatic polyamides are a known class of high performance polymers(Coprehensive Polymer Sci. Vol. 5, page 375 (1989), Encyclopedia ofPolymer Science Vol. 11, page 381 (1986); U.S. Pat. Nos. 3,063,966;3,671,542 and GB 1,246,168).

Aromatic polyamides are generally highly crystalline polymers whichoften cannot be melted without decomposition and which lave high glasstransition temperatures. They have excellent mechanical, thermal andchemical properties. The aromatic polyamide of terephthalic acid andp-phenylenediamine (formula 1) ##STR2## thus has very good mechanicalproperties and is comparable to steel on a weight basis.

However, an essential disadvantage of these materials is that they arevery difficult and expensive to process. Because of the highcrystallinity, the melting point (about 550° C.) is far above thedecomposition temperature (about 350° C.), so that thermoplasticprocessing by standard techniques such as extrusion or injection moldingis not possible.

The only possible method is therefore processing to give fibers or filmsfrom solution. Aggressive media, such as concentrated sulfuric acid,chlorosulfonic acid or nitrogen-containing solvents, such asN-methylpyrrolidone or dimethylacetamide with considerable additions ofsalts (up to 6% by weight) are often the only media which can be usedfor this purpose (DE-A-22 19 703). The content of inorganic concomitantsubstances, determined by ash analysis, is typically several thousandppm in this process (C. O. Pruneda, R. J. Morgan, R. Lim, J. Gregory, J.W. Fischer, "The Impurities in Kevlar 49 Fibers", SAMPE Journal,Sept./Oct. 1985, 17).

A better solubility can be achieved by incorporation of meta-linkages,for example by reaction of isophthaloyl chloride with m-phenylenediamine(U.S. Pat. No. 3,063,966). Although these polyamides (formula 2)##STR3## have a better solubility, they cannot be processedthermoplastically.

Thermoplastic processing is an essential prerequisite for wide use as apolymeric material.

In DSC (differential scanning calorimetry), amorphous polymers exhibit aglass transition temperature which indicates the start of cooperativechain mobility. Just above the glass transition temperature, however,the viscosity of the melt is so high (>10 000 Pa.s), that processing byinjection molding or extrusion is not possible. Only as the temperatureincreases further does the melt viscosity fall to the values necessaryfor this processing. The processing range for amorphous polymers istypically at least 100° C. above the glass transition temperature, forexample polyether sulfone having a glass transition temperature of 225°C. is processed by injection molding at 340°-360° C.

Partly crystalline polymers exhibit a melting peak in DSC, in additionto a glass transition point. Processing via the melt is thereforepossible only above the melting point. The processing temperatures aretypically about 10°-50° C. above the melting point.

The desired decrease in melt viscosity can be achieved--above all in thecase of amorphous polymers--by increasing the temperature. However, thisis counteracted by the limited thermal stability of the polymers.Although polymers can often be converted into the liquid state byincreasing the temperature, processing from the melt is thus not alwaysimplicitly associated with this. For processing via injection molding orextrusion under the usual conditions in practice, it is necessary forthe material to undergo practically no change in melt viscosity, forexample by degradation or crosslinking, over a prolonged period of timeat the processing temperature.

There has been no lack of attempts to prepare fusible polyamides whichhave high glass transition temperatures and good mechanical properties(high elasticity too dull, good tear and penetration strengths) andwhich furthermore allow thermoplastic processing by the standardtechniques.

Aromatic polyamides which have flexibilizing ether groupings in thediamine portion, are capable of flow and can be shaped in the melt aredescribed in DE-A-26 36 379 (U.S. Pat. No. 4,278,786). The flowabilityof an aromatic polyamide of isophthaloyl dichloride, terephthaloylchloride and 2,2-bis 4-(4-aminophenoxy)phenyl!propane, which has areduced viscosity of 0.81 dl/g, is thus 5.6×10⁻³ cm³ /s at temperaturesin the range from 250° to 300° C. under a load of 300 kg. However,processing of these polymers with the aid of injection molding orextrusion techniques at such low flowabilities cannot take place.

Structural variations (incorporation of meta-linkages) lead to noincrease in flowability (DE-A-26 36 379, Examples 2, 3, 4, 5; ComparisonExample E of this application). Interface condensation for thepreparation of such polyamides leads, by partial hydrolysis, to carboxyland amino groups which are located on the ends of the polymer chain andare reactive in the melt.

Aromatic polyamides and polyacrylates which can be processed from themelt are described in EP-A-263 593.5-tert-Butylisophthalic acid isemployed as the acid component. The disadvantage of the materialsdescribed here lies mainly in their inadequate heat resistance, sincethe aliphatic side chain tends to undergo side reactions at highertemperatures, leading to a drastic change in melt viscosity.

Thermoplastically processable aromatic polyether amides which, forexample, can be pressed or ram-extruded to give sheets are furthermoreknown (DE-A-38 18 208 (U.S. Ser. No. 357 527) and DE-A-38 18 209 (U.S.Ser. No. 358 180)). Solution condensation of the aromatic dicarboxylicacid chloride with the aromatic diamine is carried out using equimolaramounts in aprotic, polar solvents of the amide type. Chain-blockingagents, for example monofunctional amines or benzoyl chloride, arealready added during the polymerization operation, i.e. in the presenceof the diacid chloride, to limit the molecular weight.

Premature ending of the polymerization operation occurs in this manner,only half of the end groups reacting with the chain-blocking agent andthe other half remaining reactive. A comparable effect occurs if one ortwo different chain-blocking reagents are added after the maximumpossible molecular weight which can be achieved experimentally has beenreached (Comparison Example C of this application).

The intrinsic viscosities of these polymers lie in a range from 1.5 to 4dl/g, which corresponds to melt viscosities of more than 10 000 Pa.s, atbelow the decomposition temperature. Here also, processing by injectionmolding or extrusion is therefore not possible (see Comparison Example Bof this application).

The invention is based on the object of developing thermoplasticaromatic polyether amides which can be processed by injection molding orextrusion processes and have good mechanical properties.

The aim of the present invention is therefore to provide, from favorablestarting components, aromatic polyamides which have a high glasstransition temperature and excellent mechanical properties and can beprocessed thermoplastically, with the proviso that the aromaticpolyamides form stable melts, have melt viscosities of less than 10 000Pa.s at below the decomposition temperature and can be processed byinjection molding or extrusion.

Another aim of the present invention is to provide a process for thepreparation of aromatic polyamides which leads to products having areproducible molecular weight and stable melt viscosity properties.

Another aim of the present invention is to provide a process for shapingfilaments, fibers, films and moldings by thermoplastic processes,preferably injection molding or extrusion.

SUMMARY OF THE INVENTION

The invention relates to a thermoplastically processable aromaticpolyether amide of the formula (I) ##STR4## in which the symbols Ar,Ar', Ar₁, Ar₂, R, R', Y, x, y and z have the following meanings:

Ar is a divalent, substituted or unsubstituted, aromatic orheteroaromatic radical or a group

    --Ar*--Q--Ar*--

in which

Q is a bond or an --O--, --C(CH₃)₂, --CO--, --S--, --SO-- or --SO₂ --bridge and Ar* is an aromatic radical; the carbonyl groups of the Arradical are on non-adjacent ring carbon atoms (for example in the para-or meta-position). This is optionally substituted by one or two branchedor unbranched C₁ -C₃ -alkyl or alkoxy radicals, aryl or aryloxy radicalsor C₁ -C₆ -perfluoroalkyl or perfluoroalkoxy radicals or by fluorine,chlorine, bromine or iodine atoms, Ar being up to three differentradicals;

Ar and Ar' are independent of one another and are identical ordifferent, and Ar' has the meaning given for Ar or is an Ar--Z--Argroup. In this case, Z is a --C(CH₃)₂ -- or --O--Ar*--O--bridge.

Y is a --C(CH₃)₂ --, --CO--, --SO₂ --, --S-- or a --C(CF₃)₂ --bridge, Yin the same polymer laving up to two different meanings at the sametime;

Ar₁ and Ar₂ are identical or different from one another and are each asubstituted or unsubstituted para- or meta-arylene radical, for examplemeta- or para-phenylene, Ar₂ preferably being a para-phenylene radical.

The sum of the mole fractions (molar contents) x, y and z is one, butthe sum of x and z may not be equal to y, and x can assume the valuezero. In a preferred embodiment, z is greater than x. The molecularweight is controlled by non-stoichiometric addition of the monomers.

After the conclusion of the polycondensation reaction, the ends of thepolymer chain are closed completely by addition of at leaststoichiometric amounts of monofunctional reagents which react in thepolymer to give groups R and R' which do not react further. The endgroups R and R' here are independent of one another and are identical ordifferent, preferably identical, and are chosen from a group comprisingthe formulae V, VI, VII and/or VIII. ##STR5##

In the case of the end groups VII and/or VIII, the terminal nitrogen informula (I) is an imide nitrogen.

E in the abovementioned formulae is a hydrogen or a halogen atom, inparticular a chlorine, bromine or fluorine atom, or an organic radical,for example an aryl(oxy) group.

The aromatic polyether amide according to the invention, in which thestructure comprises the recurring units

    --CO--Ar--CO--                                             (II)

    --NH--Ar'--NH--                                            (III)

    --NH--Ar.sub.1 --O--Ar.sub.2 --Y--Ar.sub.2 --O--Ar.sub.1 --NH--(IV)

in which Ar, Ar', Ar₁, Ar₂ and Y have the abovementioned meaning, isprepared by reaction of one or more dicarboxylic acid derivatives withone or more diamines by the solution or melt condensation process, oneof the components being employed in less than the stoichiometric amountand a chain-blocking agent being added when the polycondensation hasended. In a preferred case, in each case up to three different units ofthe formulae (II), (III) and/or (IV) are employed for the preparation ofthe polyether amides according to the invention. It has been found thatthermoplastic aromatic polyether amides which have very good mechanicalproperties can be processed by conventional processes, such as, forexample, extrusion or injection molding, if

a) the molecular weight is controlled in a targeted manner by usingnon-stoichiometric amounts of the monomers,

b) the ends of the polymer chain are closed completely by monofunctionalcompounds which do not react further in the polymer, and, preferably,

c) the content of inorganic impurities in the polymer after working upand isolation does not exceed 500 ppm.

The thermoplastic aromatic polyamides prepared by the process accordingto the invention furthermore are distinguished by the fact that theyhave an average molecular weight M_(n) in the range from 5,000 to 50,000(M_(n) =absolute number average) and a low melt viscosity which does notexceed 10 000 Pa.s at the processing temperature.

Processing to give moldings, films and wires or else to give coatings iscarried out from a solution or melt, which have been prepared by thecustomary polycondensation processes, but preferably by melt or solutionpolycondensation.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

The following compounds are suitable for preparation of the polyetheramides according to the invention:

Dicarboxylic acid derivatives of the formula (IX)

    W--CO--Ar--CO--W                                           (IX)

in which Ar has the abovementioned meaning and W is a fluorine,chlorine, bromine or iodine atom, preferably a chlorine atom, or an --OHor OR" group, film which R" is a branched or unbranched aliphatic oraromatic radical.

Examples of compounds of the formula (IX) are: terephthalic acidterephthaloyl dichloride phenyl terephthalate isophthalic acid diphenylisophthalate isophthaloyl chloride phenoxyterephthalic acidphenoxyterephthaloyl dichloride diphenyl phenoxyterephthalatebis(n-hexyloxy)terephthalic acid bis(n-hexyloxy)terephthaloyl dichloridediphenyl bis(n-hexyloxy)terephthalate 2,5-furandicarboxylic acid2,5-furandicarbonyl chloride diphenyl 2,5-furandicarboxylate andcorrespondingly also the dicarboxylic acid dichlorides and diphenylesters of thiopheneticarboxylic acid naphthalene-2,6-dicarboxylic aciddiphenyl ether-4,4'-dicarboxylic acid benzophenone-4,4'-dicarboxylicacid isopropylidene-4,4'-dibenzoic acid diphenylsulfone-4,4'-dicarboxylic acid tetraphenylthiophene-dicarboxylic aciddiphenyl sulfoxide-4,4'-dicarboxylic acid diphenylthioether-4,4'-dicarboxylic acid and trimethylphenylindanedicarboxylicacid.

Suitable aromatic diamines of the formula (X)

    H.sub.2 N--Ar'--NH.sub.2                                   (X)

in which Ar'-- has the abovementioned meaning, are preferably thefollowing compounds: m-phenylenediamine p-phenylenediamine2,4-dichloro-p-phenylenediamine diaminopyridine bis(aminophenoxy)benzene1,4-bis(4-aminophenoxy)benzene 1,3-bis(4-aminophenoxy)benzene1,4-bis(3-aminophenoxy)benzene 1,3-bis(3-aminophenoxy)benzene1,2-bis(4-aminophenoxy)benzene 1,2-bis(3-aminophenoxy)benzene 2,6-bis(aminophenoxy)pyridine 3,3'-dimethylbenzidine 4,4'- and3,4'-diminodiphenyl ether isopropylidene-4,4'-dianiline p,p'- andm,m'-bis(4-aminophenylisopropylidene)benzene 4,4'- and3,3'-diaminobenzophenone 4,4'- and 3,3'-diaminodiphenyl sulfone andbis(2-amino-3-methylbenzo) thiophene S,S-dioxide.

Possible aromatic diamines are furthermore those of the formula (XI)

    H.sub.2 N--Ar.sub.1 --O--Ar.sub.2 --Y--Ar.sub.2 --O--Ar.sub.1 --NH.sub.2(XI)

in which Ar₁, Ar₂ and Y have the abovementioned meaning.

Possible aromatic diamines of the formula (XI) are:

2,2-bis 4-(3-trifluoromethyl-4-aminophenoxy)phenyl!propane bis4-(4-aminophenoxy)phenyl sulfide bis 4-(3-aminophenoxy)phenyl!sulfidebis 4-(3-aminophenoxy)phenyl!sulfone bis4-(4-aminophenoxy)phenyl!sulfone 2,2-bis4-(4-aminophenoxy)phenyl!propane 2,2-bis4-(3-aminophenoxy)phenyl!propane 2,2-bis4-(2-aminophenoxy)phenyl!propane 1,1,1,3,3,3-hexafluoro-2,2-bis4-(4-aminophenoxy)phenyl!propane.

The polyether amides according to the invention are preferably preparedby solution condensation processes.

Solution condensation of the aromatic dicarboxylic acid dichloride withthe aromatic diamines is carried out in aprotic, polar solvents of theamide type, for example N,N-dimethyl-acetamide, preferably inN-methyl-2-pyrrolidone. If appropriate, halide salts of metals of thefirst and/or second group of the Periodic Table of the Elements areadded to these solvents in a known manner in order to increase thedissolving capacity or to stabilize the polyether amide solutions.Preferred additions are calcium chloride and/or lithium chloride. In apreferred embodiment, the condensation is carried out without additionof a salt, since the aromatic polyamide described above aredistinguished by a high solubility in the abovementioned solvents of theamide type.

In contrast to the polyamide structures known to date, it has been foundin the case of the polyamides according to the invention that fusiblepolyether amides which have good mechanical properties, aredistinguished in particular by high initial moduli and good tear andpenetration strengths and allow thermoplastic processing by standardmethods can be prepared if at least one of the starting components isemployed in less than the stoichiometric amount. In this way, it ispossible to achieve a limitation of the molecular weight in accordancewith the known Carother's equation: ##EQU1## in which q 1 and at thesame time ##EQU2## P_(n) =degree of polymerization q=molar ratio of thediacid components to the amine components.

If less than tile stoichiometric amount of acid dichloride is used, amonofunctional aromatic acid chloride or acid anhydride is added as thechain-blocking agent at the end of the polymerization reaction, forexample benzoyl chloride, fluorobenzoyl chloride, diphenylcarbonylchloride, phenoxybenzoyl chloride, phthalic anhydride, naphthalicanhydride or 4-chloronaphthalic anhydride.

Such chain-blocking agents can be optionally substituted, for example byfluorine or chlorine atoms. Benzoyl chloride or phthalic anhydride ispreferably employed, particularly preferably benzoyl chloride.

If less than the stoichiometric amount of the diamine component is used,a monofunctional, preferably aromatic amine is employed as achain-blocking agent at the end of the polycondensation, for examplefluoroaniline, chloroaniline, 4-aminodiphenylamine, aminobiphenylamine,aminodiphenyl ether, aminobenzophenone or aminoquinoline.

In a particularly preferred embodiment of the polycondensation process,the diacid chloride in less than the stoichiometric amount is subjectedto polycondensation with the diamine, and the reactive amino groupswhich remain are then deactivated with a monofunctional acid chloride ordiacid anhydride.

In another preferred embodiment, the diacid chloride is employed in lessthan the stoichiometric amount and is subjected to polycondensation witha diamine. The reactive amino end groups which remain are thendeactivated with a monofunctional, preferably aromatic, optionallysubstituted acid chloride or acid anhydride.

The chain-blocking agent, that is to say monofunctional amine or acidchloride or acid anhydride, is preferably employed here in astoichiometric amount or more than the stoichiometric amount, based onthe diacid or diamine component.

The molar ratio q (acid component to diamine component) for preparationof the aromatic polyamides according to the invention can be varied inthe range from 0.90 to 1.10, exact stoichiometry (q=1) of thebifunctional components being excluded. The molar ratio is particularlypreferably in the range from 0.90 to 0.99 and 1.01 to 1.10, particularlypreferably in the range from 0.93 to 0.98 and 1.02 to 1.07, especiallyin the range from 0.95 to 0.97 and 1.03 to 1.05.

The polycondensation temperatures are usually in the range from -20° to+120° C. preferably from +10° to +100° C.

Particularly good results are achieved at reaction temperatures of +10°to +80° C. The polycondensation reactions are preferably carried outsuch that 2 to 40, preferably 5 to 30% by weight of polycondensate arepresent in the solution after conclusion of the reaction. For specificuses, the solution can be diluted, if required, withN-methyl-2-pyrrolidone or other solvents, for example dimethylformamide,N,N-dimethylacetamide or butylcellosolve, or concentrated under reducedpressure (thin film evaporator).

When the polycondensation has ended, the hydrogen chloride formed, whichis loosely bonded to the amide solvent, is removed by addition ofacid-binding auxiliaries. Auxiliaries which are suitable for thispurpose are, for example, lithium hydroxide, calcium hydroxide and, inparticular, calcium oxide, propylene oxide, ethylene oxide or ammonia.In a particular embodiment, pure water, which dilutes the hydrochloricacid and at the same time serves to precipitate the polymer, is used asthe "acid-binding" agent. For production of shaped structures accordingto the present invention, the copolyamide solutions according to theinvention which are described above are filtered, degassed and furtherprocessed in the known manner described below.

If appropriate, suitable amounts of additives are also added to thesolutions. Examples are light stabilizers, antioxidants, flameproofingagents, antistatics, dye-stuffs, colored pigments, fillers or polymers,such as, for example, polytetrafluoroethylene.

For isolation of the polyether amide, a precipitant can be added to thesolution and the coagulated product can be filtered off. Typicalprecipitants are, for example, water, methanol and acetone, which mayalso contain pH-controlling additions, such as, for example, ammonia oracetic acid, if appropriate.

The isolation is preferably carried out by comminution of the polymersolution with an excess of water in a cutting mill. The finelycomminuted coagulated polymer particles facilitate the subsequentwashing steps (removal of the secondary products formed from thehydrogen chloride) and the drying of the polymer (avoidance ofinclusions) after filtration. Subsequent comminution is alsounnecessary, since a free-flowing product is formed directly.

In addition to the solution condensation described, which is a readilyaccessible process, other customary processes can also be used for thepreparation of polyamides, such as, for example, melt or solidscondensation, as already mentioned. In addition to condensation withregulation of the molecular weight, these processes can also comprisepurification or washing steps and the addition of suitable additives.The additives moreover can also be added subsequently to the isolatedpolymer during thermoplastic processing.

The aromatic polyamides according to the invention have surprisinglygood mechanical properties and high glass transition temperatures.

The Staudinger index η!_(o) is in the range from 0.4 to 1.5 dl/g,preferably in the range from 0.5 to 1.3 dl/g, particularly preferably inthe range from 0.6 to 1.1 dl/g. The glass transition temperatures are ingeneral above 180° C., preferably above 200° C., and the processingtemperatures are in the range from 320° to 380° C., preferably in therange from 330° to 370° C., particularly preferably in the range from340° to 360° C.

Processing of the polyphides according to the invention can be carriedout by injection molding or extrusion processes, since the meltviscosities do not exceed 10 000 Pa.s at the processing temperature.

Possible suitable apparatuses are conventional injection moldingmachines with locking forces of 60 to 120 t and injection pressures of1000 to 2000 bar. The extrusion can be carried out on customary single-or twin-screw extruders.

The polyether amides according to the invention are suitable for theproduction of a large number of moldings, such as bearing components,seals, closures, clips, electrical insulators, electrical plugs,housings for electrical components, car body components in motor vehicleconstruction, pistons, gearwheels, turbine blades, impeller blades,thread guides, camshafts, brake linings and clutch disks.

Threads, fibers or pulp of the copolyether amides according to theinvention can be used, for example, as reinforcing materials for rubber,thermoplastics or thermo-setting resins, for the production of filterfabrics or as a lightweight insulating material. Foams of hightemperature resistance can be produced by addition of gas-supplyingadditives.

Films and paper are suitable as heat-resistant insulating material;films in particular as a substrate for flexible printed circuit boardsand for use in the data processing sector.

The polyether amides according to the invention and the moldingsproduced therefrom have been tested by the following test methods:Staudinger index η!_(o)

The Staudinger index η!_(o) is defined according to equation 1: ##EQU3##in which η and η₁ are the viscosities of the solution and solventrespectively and c₂ is the concentration of the polymer. The measurementwas carried out in N-methylpyrrolidone at 25° C.

Mechanical properties

The tear strength, elongation at tear, tensile stress at yield,elongation at yield and elasticity modulus (E modulus) were determinedwith the aid of tensile stress/elongation apparatuses of the Instronbrand at 23° C. under 50% relative atmospheric humidity.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a graph of torque versus time for a polymer according to theinvention;

FIG. 2 is a graph of torque versus time for a comparison polymer;

FIG. 3 is a graph of zero shear melt viscosity versus molecular weight;and

FIG. 4 is a graph of torque versus time for a copolymer according to theinvention.

EXAMPLES

The following abbreviations have been used in the examples:

    ______________________________________    BAB =     2,2-bis 4-(4-aminophenoxy)phenyl!propane    TPC =     terephthaloyl chloride    IPC =     isophthaloyl chloride    FDC =     2,5-furandicarbonyl chloride    FBC =     4-fluorobenzoyl chloride    BCl =     benzoyl chloride    NMP =     N-methylpyrrolidone    CaO =     calcium oxide    E modulus =              elasticity modulus    MFI =     melt flow index    DSC =     differential scanning calorimetry (dynamic              thermal analysis)    M.sub.w = weight-average molecular weight    M.sub.n = number-average molecular weight    D = M.sub.w /M.sub.n =              molecular dispersity, heterogeneity, molecu-              lar weight distribution    TGA =     thermogravimetric analysis    T.sub.g = glass transition temperature (determined as              the point of inflection in the glass stage in              DSC)    PS =      polystyrene, M(PS) = apparent molecular              weight, determined by GPC in relation to              polystyrene    PO =      1,2-propylene oxide    BAPS =    bis 4-(4-aminophenoxy)phenyl! sulfone    GPC =     gel permeation chromatography    PA =      phthalic anhydride    E water = deionized water    UL 94 =   Underwriters Laboratories (U.S.A.) Bulletin 94              (test standard for combustibility)    MH =      Mark-Houwink equation:  η!.sub.o  = k · M.sub.w.sup              .a     η!.sub.o =              Staudinger index, unit dl/g    η.sub.m =              melt viscosity, unit Pa.s    DMF =     dimethylformamide    DMAC =    N,N-dimethylacetamide    ______________________________________

EXAMPLE 1

Polyether amide from 2,2-bis 4-(4-aminophenoxy)phenyl!propane,terephthalic acid and benzoyl chloride in N-methylpyrrolidone:

4105 g (10 mol) of BAB were dissolved in 15.24 l of NMP in an enameled40 l stirred tank with a heating jacket under nitrogen. Aftercontrolling the temperature at 25° C., 1959 g (9.65 mol=96.5%) of TPC,dissolved in 5 l of NMP, were added. 30 minutes after 70° C. wasreached, 112.5 g (0.8 mol) of BCl were added, the mixture was cooled to60° C. a further 30 minutes later, and 566 g (10.1 mol) of CaO as asuspension in 305 g of NMP were added. After 1 hour, the clear, viscoussolution was drained off, diluted from 20% to approximately 13% polymercontent with about 13 l of NMP and filtered under an N₂ pressure of 3bar, and the product was finally precipitated as a fine powder (particlesize ≦1 mm) with water. The polymer powder was washed four times for ineach case 2 hours with 60 l of fresh E water at 95°-98° C. in a stirredpressure filter, coarsely dried in a hot stream of nitrogen and washedtwice more with 60 l of acetone (2 hours, 60° C.). It was predriedovernight in a stream of nitrogen, and then thoroughly dried at 130° C.(100 mbar) for 14 hours and finally at 150 ° C. (<10 mbar) for 8 hours.Yield 5.0 kg (93%). η!₀ =1.06 dl/g; M_(w) =40,000 g.mol⁻¹ ; ash content:200 ppm; GPC:M_(w) (PS)=49,000 g.mol⁻¹, M_(n) (PS)=50,000, D=2.1. Themelt stability was tested in a kneading experiment (FIG. 1).

The free-flowing polymer powder was shaped to a 2 mm melt strand underan argon inert gas atmosphere in a twin-screw extruder (Haake RheoeordSystem 90 with twin-screw extruder TW 100 and die diameter 1 mm) at atemperature zone setting of 310°/320°/330°/340° C., the last figurecorresponding to the die temperature, and a melt temperature of 360° C.,the strand being injection molded after granulation and renewed thoroughdrying (150° C., <10 mbar, 8 hours).

Apparatus and conditions: KRAUSS MAFFEI 90/340 A, locking force 900 kN,screw diameter 35 (20D), die temperature 350° C., mold temperature 180°C. injection pressure 1500 bar (4 seconds), after-pressure 1200 bar (12seconds), total cycle time 35 seconds.

The following properties were measured on the resulting shaped articles:

Density: 1.22 g.cm⁻³

Water uptake: 2.3% (23° C., 85% relative atmospheric humidity)

Elongation at break: 6%

Tensile E modulus: 3.4 GPa (tensile bar No. 3, DIN 53 455)

Flexural E modulus: 3.2 GPa

Notched impact strength: 83 J/m

Impact strength: 281 J/m

Ball indentation hardness: 162 Pa

MFI (340° C., 10 kg): 15 ccm/10 minutes

Tg=210° C. (DSC)

Combustibility (UL-94): V-O (0.8 mm), i.e. most favorable combustibilityclass, even without flameproofing additives

Comparison Example A

Polyether amide from BAB and TPC without addition of BCl:

314.1 g (0.7651 mol) of BAB were dissolved in 1,264 g of dry NMP undernitrogen. After cooling to -10° C., 155.5 g (0.7659 mol) of TPC wereadded, while stirring. The mixture was further stirred at -10° C. forone hour, the cooling bath was then removed and, when room temperaturehad been reached, the mixture was stirred for a further 3 hours. 766 gof DMF were added to the viscous polymer solution and the mixture washomogenized, while stirring. The polymer was precipitated in aprecipitating bath of 5 kg of ethanol and 20 l of water, while stirring,filtered off and washed intensively several times with hot E water. Thecolorless polymer was dried intensively, finally at 120° C. in vacuo(<10 mbar) for 8 hours. The Staudinger index was η!_(o) =2.45 dl/g⁻¹,corresponding to M_(w) =170,000 g.mol⁻¹.

GPC: M_(n) (PS)=189,000 g/mol; D=6.1.

Ash content=2,700 ppm

60 g were investigated in a kneading experiment under an argon inert gasatmosphere at 360° C. After 3 minutes, the torque falls to 10% of themaximum value (FIG. 2). After 6 minutes, the torque has fallenpractically to zero. After 30 minutes, a black-brown, crumbly mass whichshowed no signs of a melting process was removed.

Comparison Example B

Polyether amide from BAB and TPC without addition of benzoyl chloride(BCl)

164.21 g (0.4 mol) of BAB were dissolved in 2,193 g of NMP undernitrogen, and 81.21 g (0.4 mol) of TPC were added at between 15° and 70°C. in the course of about 60 minutes. The viscous and clear solution wassubsequently stirred at 70° C. for about a further 40 minutes, thenneutralized with 24.54 g (0.438 mol, 96% pure) of CaO and subsequentlystirred at 70° C. for a further 30 minutes. The solution was filtered,and coagulated and comminuted in a cutting mill (manufacturer: Condux),with addition of water. The polymer which had precipitated was washedfive times with desalinated water and then twice with acetone. Dryingwas carried out at 130° C. in vacuo under 50-80 mbar with gentlecovering with nitrogen.

Staudinger index η!_(o) 4.2 dl/g, M_(w) =400,000 g.mol⁻¹

Ash content: 3,200 ppm

DSC: glass transition temperature Tg=230° C.,

TGA: significant weight loss at 400° C.

In kneading experiments under an argon inert gas atmosphere at 340° C.,350° C. and 360° C., a black-brown, porous/brittle mass which showed novisible traces of a melting operation was removed in each case a fewminutes after in each case 60 g had been introduced completely.

EXAMPLES 2-7

In an analogous manner to that in Example 1, 4105 g (10 mol) of BAB werereacted with 1949 g (9.6 mol=96%) of TPC or isophthaloyl chloride and126.5 g (0.9 mol) of BCl in 20.8 kg of NMP:

    ______________________________________         TPC/    Staudinger From GPC         IPC     index      M.sub.n      M.sub.w from                                                T.sub.g.sup.b)    Ex.  ratio    η!.sub.o /dl/g                            (PS)    D    MH     /°C.    ______________________________________    2    1/0     0.86       39,000  2.1  36,000 227    3    8/2     0.69       34,000  2.2  26,000 221    4    7/3     0.68       32,000  2.2  25,000 224    5    6/4     0.68       36,000  2.1  25,000 222    6    5/5     0.68       35,000  2.0  25,000 226    7.sup.a)         7/3     0.80       44,000  2.0  32,000 227    ______________________________________     .sup.a) Example 7 as Example 4, but TPC/BAB = 965/1000 (molar ratio)     .sup.b) Polymers 3-7 are amorphous in Xrays.

The products were extruded on an extruder of the Leistritz brand (TypeLSM 30.34 GH) under the conditions described below (40 revolutions perminute). Injection molding as described in Example 1 resulted in thefollowing mechanical properties:

    __________________________________________________________________________       Melt           Back Through-                     MFI.sup.a)                         E    Elongation                                     Tear                                         Yield      Notched       temp.           pressure/                put  340° C.                         modulus/                              at     stress/                                         Elongation/                                                Stress/                                                    impact    Ex.       die/°C.           bar  kg/h 5 kg                         GPa  tear/% MPa %      MPa strength/mJ    __________________________________________________________________________    2  336 45   1.9  4   2.6  6      87             81/J/m.sup.b)    3  339 15   1.7  6   2.5  21     76  9      86  220    4  331 30   2.3  7   2.5         64             210    5  334 30   2.4  8   2.4         74             210    6  335 35   3.1  11  2.5         78             200    7  335 30   2.3  4   2.5  27     75  8      89  200    __________________________________________________________________________     .sup.a) Melt flow index in dg/minute     .sup.b) Impact strength 281 J/m

The resistance to solvents was tested on a standard test specimen (No.3). After storage in chloroform for days, the test specimen had taken up5.7% by weight of the solvent. The tear stress was increased to 81 MPa,while the other mechanical properties remained unchanged.

EXAMPLE 8

Polyether amide from BAB, TPC, 4-fluorobenzoyl chloride and1,2-propylene oxide in NMP:

246.3 g (0.6 mol) of BAB were dissolved in 1615 g of dry NMP undernitrogen. 118.16 g (0.582 mol=97%) of TPC were added at 10° C. Afterheating to 50° C. (about 0.5 hour), 5.7 g (36 mmol=6%) of FBC wereadded. 40 minutes later, a mixture of 73.2 g (1.26 mol) of PO and 88 gof NMP were added dropwise via a dropping funnel. After filtration, theproduct was precipitated in desalinated water (E water), and washed outseveral times with hot E water and then several times with acetone.After predrying under about 100 mbar, it was finally dried at 150° C.under <10 mbar for 8 hours.

Ash content: 460 ppm.

EXAMPLE 9

287.4 g (0.7 mol) of BAB were dissolved in 1708 g of dry NMP undernitrogen. 139.27 g (0.686 mol=98%) of TPC were added at 3° C. Afterheating to 50° C., 5.6 g (35 mmol=5%) of FBC were added. 1 hour later, amixture of 85.4 g (1.47 mol) of PO and 88 g of NMP was added dropwisevia a dropping funnel. Working up was carried out analogously to Example8.

Ash content: 350 ppm.

EXAMPLE 10

Polyether amide from BAB, TPC, isophthaloyl chloride, FBC and PO in NMP:

410.5 g (1.0 mol) of BAB were dissolved in 1816 g of dry NMP undernitrogen. A homogeneous mixture of 99.48 g each of TPC and IPC (in eachcase 0.49 mol, together 0.98 mol=98%) was added at 5° C. and rinsing wascarried out with 100 ml of NMP. After the internal temperature hadreached 50° C. (about 0.5 hour), 6.34 g (40 mmol=4%) of FBC were added.1 hour later, a mixture of 122 g (2.1 mol) of PO and 147 g of NMP wasadded dropwise. Working up was carried out analogously to Example 8.

Ash content: 100 ppm.

Comparison Example C shows that no end group control is possible if theend group-closing reagents are added to a polymer having the maximummolecular weight which can be achieved experimentally.

129.75 g (0.316 mol=100%) of BAB were dissolved in 2110 g of dry NMP.60.96 g (0.300 mol=95%) of TPC were first added at 15° C. When themixture had reached 70° C., a further 3.8 g (18.7 mol, together 100.29%)of TPC were added in portions until no further rise in the viscosity ofthe polymerization solution was observed. 0.95 g (6 mmol=1.9%) of FBCwas added and the mixture was subsequently stirred at 70° C. for 80minutes. 0.67 g (6 mmol=1.9%) of 4-fluoroaniline was then added. 80minutes later, 34.96 g (0.623 mol) of CaO were added. After 1 hour at70° C., the mixture was filtered and the product was worked up as inExample 8.

                  TABLE    ______________________________________    Examples 8-10 and Comparison Example C                                        Fluorine                                               Ash         Molar                          content                                               con-         ratio                   % F    calcula-                                               tent/    Ex.  q        η!.sub.o.sup.a)                        % F (NMR).sup.b)                                 (EA).sup.c)                                        ted/%.sup.d)                                               ppm    ______________________________________    8    97      1.10   0.195 + 0.010                                 0.18   0.21   460    9    98      1.40   0.157 + 0.008                                 0.14   0.14   350    10   98      1.35   0.135 + 0.007                                 0.11    C.sup.e)         100     3.0    <0.01%.sup.f)                                 <0.01.sup.f)                                        0.03    ______________________________________     .sup.a) Staudinger index in dl/g     .sup.b) Measured as 4fluorobenzamide end group in the .sup.19 FNMR     spectrum     .sup.c) Elemental analysis (EA)     ##STR6##     ##STR7##     .sup.e) Polymer decomposes to a black mass on heating     .sup.f) Below the detection limit

79-100% of the fluorine from the 4-fluorobenzamide end groups was foundin polymers 8-10 according to the invention. No fluorine was to be foundin Example C, which is not according to the invention, i.e. less than33% of the polymer end groups carried fluorine (incomplete end groupclosure).

EXAMPLES 11, 12, 13

This series of experiments shows that an excess of end group-closingreagent (here BCl) is harmless to the fusible polymer.

    ______________________________________    Example %.sup.a)                    η!.sub.o /dl/g                               M.sub.n (PS)/gmol.sup.-1                                          D    ______________________________________    11      8      0.95 ± 0.04                               62,000     1.81    12      9      0.96 ± 0.04                               63.000     1.82    13      10     1.03 ± 0.05                               61,000     1.83    Average /      0.98        62,000     1.82    ______________________________________     .sup.a) Mol percent of end groupclosure reagent benzoyl chloride (BCl); 7     = stoichiometric

The studies showed--within the measurement accuracy--no differencebetween polymers 11, 12 and 13. The samples also behaved comparably inthe measurement kneader at 340° C.

EXAMPLE 11

410.5 g (1.0 mol=100%) of BAB were initially introduced into 2009 g ofdry NMP under nitrogen, and 195.91 g (0.965 mol=96.5%) of TPC wereadded. The mixture was heated first to 50° C. and then to 70° C. (about0.5 hour). After addition of 11.24 g (0.08 mol=8%) of BCl, stirring wascontinued at 70° C. for 30 minutes, and a liquid mixture of 128 g of POand 154 g of NMP was finally added dropwise. Working up was carried outas described in Example 8.

Ash content: 98 ppm

EXAMPLE 12

Procedure as in Example 11; however, instead of 8% of BCl, 9%=0.09mol=12.65 g of BCl was added here.

EXAMPLE 13

Procedure as in Example 11; however, instead of 8% of BCl, 10%=0.1mol=14.57 g of BCl were added here. Ash content: 59 ppm

EXAMPLE 14

Polyether sulfone-amide from bis 4-(4-aminophenoxy)phenyl! sulfone, TPC,IPC and BCl in NMP:

As Example 1, but with the following starting substances: 3676 g (8.5mol) of BAPS (purity 98.6%) in each case 828.3 g (4.08 mol) of IPC andTPC (8.16 mol=96%) 106.8 g (0.76 mol=9%) of BCl and 518 g (9.24 mol) ofCaO in a total of 18,270 g of NMP instead of acetone, which acts as aplasticizer, methanol was used for rinsing.

Staudinger index: η!_(o) =0.81 dl/g

GPC: M_(n) (PS)=56,000 g/mol; D=M_(w) /M_(n) =2.2

Comparison Example D shows the adverse influence of ionic impurities onfusibility.

A mixture of the stable acetylacetonates of the following ions wereadded to a polymer prepared according to Example 11, which had an ashcontent of <500 ppm and showed no drastic change within 30 minutes in akneading test at 340° C. under an inert gas, such that the followingimpurity concentrations in ppm resulted in the polymer: 330 Fe, 130 Cr,130 Ni, 10 Mo, 10 Mn, 10 Cu, 10 Co, 10 V.

A glossy black decomposed mass was obtained within a few minutes in thekneading experiment at 340° C. and could no longer be dissolvedcompletely in NMP.

EXAMPLES 15 AND 16

Two polymer batches, prepared according to Example 8 but with 96% ofTPC, were extruded under argon under otherwise identical conditions.

    __________________________________________________________________________                     Staudinger index/dl/g       Heating zones.sup.a)                     before                          after                               extruded after a    Ex.       °C.                T.sub.melt /°C.                     extrusion                          extrusion                               standing time of 20 mins.    __________________________________________________________________________    15 310/320/330/340                360  0.83 0.58 0.60    16 330/340/350/360                380  0.74 0.66 0.57    __________________________________________________________________________     .sup.a) The last entry indicates the particular die temperature.

All the extruded samples--including those which had additionally stoodin the extruder at temperatures of 360° to 380° C. for 20 minutes--showa yellow-brown coloration. The specimen strands of about 2 mm thicknessare mechanically strong, i.e. they can be broken manually only witheffort--preferentially at gas inclusions.

EXAMPLE 17

Phthalic anhydride as chain-blocking agent

Polyether aramide from BAB, TPC and phthalic anhydride and PO in NMP:

410.5 g (1.0 mol=100%) of BAB were initially introduced into 2020 g ofdry NMP at 3° C. under nitrogen, and 196.93 g (0.97 mol=97%) of TPC wereadded. The mixture was then heated to 50° C., while stirring wascontinued, and 8.89 g (0.06 mol=6%) of PA were added. 1 hour later, amixture of 118 g of PO and 143 g of NMP was added dropwise. Afterworking up as described in Example 8 and additional drying at 200° C. (3hours), 505 g (93%) of a colorless polymer powder which had thefollowing properties were obtained:

Staudinger index: η!_(o) =1.1 dl/g

GPC: M_(n) (PS)=66,000 g/mol; D=M_(w) /M_(n) =2.4

The 300 MHz ¹ H-NMR spectrum and the corresponding ¹³ C-NMR spectrum(solvent DMSO-d₆) had the following signals characteristic of thephthalimido end group: 7.86-7.96 ppm (m, 2 mol %) and 124, 132, 135 and167 ppm. Within the measurement accuracy, all the end groups are presentin the form of the phthalimide. The kneading test at 340° C. showed nodecomposition of the melt after 30 minutes.

EXAMPLE 18a

Polyether amide using NH₃ gas as a neutralizing agent

Example 11 was repeated, with the difference that NH₃ gas was passedinto the solution 30 minutes after BCl had been added, and 50 ml ofglacial acetic acid were added after a further 30 minutes in order tobuffer the NH₃ excess. The NH₄ Cl which had precipitated was filteredoff and the product was worked up--as already described in Example 8.

Staudinger index: η!_(o) 0.96 dl/g

GPC: M_(n) (GPC)=53,000 g/mol; D=2.1

Ash content: 156 ppm.

EXAMPLE 18b

Polyether amides using water as the HCl-binding agent

Example 11 was repeated, but no neutralizing agent was added, and thehydrochloric acid polymer solution was directly added dropwise to Ewater from a glass dropping funnel. The water thus served not only toprecipitate the polymer but also to bind the resulting HCl as aqueousdilute hydrochloric acid. After working up as in Example 8, an ashcontent of 30 ppm was determined.

EXAMPLE 18c

The following data were measured on 8 samples of the terephthalamide of2,2-bis 4-(4-aminophenoxy)phenyl!propane prepared according to theabovementioned examples:

    ______________________________________     η!.sub.o /dl/g             M.sub.w /d/mol.sup.a)                         M.sub.w (PS)/g/mol.sup.b)                                      η.sub.m /Pa.s.sup.c)    ______________________________________    0.64      23,000     73,000       2,000    0.82      33,000     64,000       3,000    0.96      42,000     95,000       8,000    1.08      50,000     127,000      20,000    1.65      82,000     --           --    2.00     130,000     --           500,000    2.25     143,000     --           --    2.61     185,000     --           about 10.sup.6    ______________________________________     .sup.a) Light scattering measurement gives the absolute molecular weight     .sup.b) GPC measurement gives the molecular weight in relation to     polystyrene     .sup.c) Zero shear viscosity in the melt at 340° C.

By plotting the zero shear melt viscosity at 340° C. on a graph againstthe molecular weight (FIG. 3), it can immediately be seen that polymersof M_(w) >80,000, i.e. M_(n) >20,000-40,000, depending on theinhomogeneity, corresponding to η!_(o) >1.5 dl/g do not givecompositions which can be shaped by normal injection molding. Inparticular, below about η!_(o) 1.1 dl/g (M_(w) =50,000), polymers havingmelt viscosities of less than 10,000 Pa.s which can be processed byinjection molding without major processing problems are obtained.

EXAMPLE 19

Copolymer with a second diamine

Example 8 was repeated; however, 20 mol % of the BAB were replaced by4,4'-diamino-3,3'-dimethylbiphenyl and FBC was replaced by BCl. Thepolymer, which was worked up and dried as in Example 8, had a glasstransition temperature (DSC) T_(g) of 228° C. Staudinger index: η!_(o)=1.09 dl/g, which corresponds to M_(w) =51,000 g/mol. GPC: M_(n) =66,000g/mol; D=2.1. Homogeneous pressed sheets were obtained at 320° C. undera pressure of initially 10 bar (10 minutes) and 210 bar (5 minutes).Thereafter, 60 g of the powder were investigated in a measurementkneader under argon at 340° C. for 25 minutes at 100 revolutions perminute. The measurement curve plotted (FIG. 4) initially showsvariations in the torque which originate from the filling operation. Therise to the maximum value corresponds to the plasticizing operation, andthe curve finally becomes a practically constant plateau. Thiscorresponds to a complete, stable melt. The massive polymer piecesobtained after this treatment are almost completely soluble in NMP, butdo not change in methylene chloride.

EXAMPLES 20-25

Aramides were prepared from BAB and 2,5-furandicarbonyl dichloride, asone of the acid components, in accordance with the abovementionedexamples.

    ______________________________________          % of   % of   % of Molar ratio    Neutralizing    Ex.   FDC    IPC    TPC  q/%      BCl/% agent    ______________________________________    20    50     --     50   97       6     PO    21    100    --     --   94.5     12    CaO    22    50     --     50   97       8.8   CaO    23    100    --     --   97       6     CaO    24    100    --     --   95       10    CaO    25    20     20     60   96.5     8     CaO    ______________________________________

Transparent sheets could be pressed from the polymer powders of Examples20-25 at 340° C. without problems. In DSC, Example 20 shows a glassstage at 230° C. and no (re)crystallization, i.e. mainly amorphouspolymers are present.

The polymer powders from Example 21 and Example 23 were extruded underthe conditions described in Example 1. Extrusion at 40 and 80revolutions per minute was carried out without problems, although meltfracture initially occurred in Example 23. Smooth, brown and transparentstrands, which could be processed to granules after cooling in water,were obtained.

EXAMPLE 26

Polyether amide from 2,6-naphthalenedicarbonyl dichloride (NDC) and BAB

410.5 g (1.0 mol) of BAB were dissolved in 2051 g of dry NMP undernitrogen. 244.3 g (0.965 mol) of NDC were added at 5° C. The internaltemperature initially rose to 35° C.; the mixture was then heated to 70°C. 60 minutes later, 11.8 g (0.084 mol) of BCl were added and, after afurther 30 minutes, 62 g (1.1 mol) of CaO were added as a suspension in33 g of NMP. The mixture was subsequently stirred for 90 minutes andworked up as in Example 8.

The analytical results are summarized in the following table.

EXAMPLES 27-31

Copolyether amides from NDC and other diacid chlorides

Analogous to Example 26, but the BAB was initially introduced into 1200g of NMP and the homogeneous solution of the acid chlorides shown in thefollowing table in 763 g of NMP was added. The resulting polymer sampleswere pressed to sheets in vacuo (340° C.: heating up for 10 minutes,pressing pressure of 100 bar for 2 minutes). The yellowish sheets, whichare free from gas bubbles, are mechanically stable and show flow traceswhich suggest good processability of the melt.

    __________________________________________________________________________    % of   % of               % of                   % of       GPC evaluation                                        DSC    Ex.       NDC TPC IPC FDC  η!.sub.o /dl · g.sup.-1                              M.sub.n (PS standard) D                                        Tg.sup.a)                                           Tg.sup.b)    __________________________________________________________________________    26 100 0   0   0   1.13 ± 0.01                              43,000                                   2.9  229                                           228.sup.c)    27 50  50  0   0   0.83 ± 0.01                              35,000                                   2.4  226                                           225    28 50  0   50  0   0.85 ± 0.05                              31,000                                   2.7  226                                           226.sup.d)    29 70  0   30  0   0.89 ± 0.01                              42,000                                   2.3  228                                           228    30 70  0   0   30  0.80 ± 0.03                              41,000                                   2.3  227                                           228    31 331/3           0   331/3                   331/3                       0.83 ± 0.05                              38,000                                   2.2  223                                           227    __________________________________________________________________________     .sup.a) Glass transition temperature of the polymer powder     .sup.b) Glass transition temperature of the pressed sheet (vacuum,     340° C., 15 minutes: 0 bar; 5': 100 bar)     .sup.c) Additionally a weak melting peak at 350°  C. (1.1 J/g)     .sup.d) Additionally a weak melting peak at 335° C. (0.5 J/g)

EXAMPLE 32

Copolyether amide from TPC, BAB and 2,2-bis(4-aminophenyl)propane (PBA)

Analogously to Example 26, but 246.3 g (0.6 mol) of BAB were initiallyintroduced into 2030 g of NMP with 135.6 g (0.6 mol). of PBA, andpolycondensation was carried out with 235.1 g (1.158 mol=96.5%) of TPC.Finally, 14.2 g (0.11 mol) of BCl, and lastly 74 g (1.3 mol) of CaO,suspended in 40 g of NMP, were added. After working up as described inExample 8, the following values were measured:

Staudinger index: η!_(o) =0.82±0.01 dl/g

GPC: M_(n) (PS): M_(n) =35,000 g/mol; D=2.2.

The polymer powder could be pressed in vacuo to give a translucent,flexible sheet (340° C.): heating up time 10 minutes, pressing time 2minutes under a pressing pressure of 100 bar. DSC analysis gives a glasstransition temperature T_(g) of 258° C. (amorphous). The pressed sheetshows the same properties, from which a good melt stability of thepolymer may be concluded.

Comparison Example E demonstrates that polymers of the same empiricalcomposition as Examples 3-7 of this application prepared by interfacecondensation and therefore without a molecular weight control andefficient end group blocking lead to a material which is notthermoplastically processable.

Comparison Example E

Equimolar ratio of acid to amine component, interface condensation,variation of the TPC/IPC ratio.

A solution of 76.30 g (1.907 mol) of NaOH and 0.82 g (7.5 mmol) ofhypophosphorous acid in 800 g of ice was mixed thoroughly with asolution of 328.4 g (0.8 mol) of BAB in 1.2 kg of dry cyclohexanone in aWarring blender. A solution of 182.41 g (0.8 mol) of the particularmixture of TPC and IPC in 1.2 kg of cyclohexanone were added to thismixture with vigorous mixing, and rinsing was carried out with 100 g ofcyclohexanone. The mixture was cooled externally with ice-water, whilestirring further, in order to keep the temperature at 2°-5° C. After 3hours, 6.0 g (0.043 mol) of benzoyl chloride, dissolved in 100 g ofcyclohexanone, were introduced and the mixture was heated to roomtemperature in the course of about 1 hour. After a further 2 hours atroom temperature, the pasty mass was treated with about twice the volumeof methanol and the polymer powder precipitated out in this way wasworked up further as described in Example 1, careful attention beingpaid to complete removal of the residual cyclohexanone under an oil pumpvacuum-- finally at 200° C.

The following analytical data were determined on the polymers thusprepared, which are not according to the invention:

    ______________________________________    Comparison             η!.sub.o   GPC    Example     TPC/IPC   dl/g     M.sub.n                                          D    ______________________________________    E-3         2/8       3.8      236,000                                          14    E-4         3/7       1.9      88,000 4.4    E-5         4/6       2.5      99,000 4.3    E-6         5/5       2.1      89,000 4.0    ______________________________________

All four polymer samples resulted in dark brown to black, crumblymaterials, which were evidently decomposed, without signs of a melt,within 4-10 minutes in a kneading test under an argon inert gasatmosphere (60 g, 340° C.). More extensive thermoplastic processing, forexample extrusion, was not possible under these circumstances.

General comments on the analysis of the polymers:

Kneaders can be employed to characterize the polymers, especially themelt viscosity and the stability of the melt with respect to time(kneader/measurement extruder: HAAKE Rheocord System 90 with a kneadingchamber at 400° C. and a twin-screw extruder TW 100). The torque of thekneader is usually plotted against time. The shape of the curve allowsconclusions on the stability of the melt to be drawn.

Absolute measurement of the melt viscosity can be carried out incommercially obtainable viscometers, for example capillary viscometersor plate/plate viscometers (Gottfert materials testing machine, meltindex tester, model MPS-D; Rheometrics Dynamic Spectrometer System 4with plate/plate geometry, N₂). In addition to the important informationon the dependence of the melt viscosity on the shear rate, thesemeasurements also allow evaluation of the stability of the melt.

Use Examples

A. Metal coating from a solution of the polyether aramide

The polycondensation solution from Example 8 was applied to in each case3 wires of copper or high-grade steel which had first been degreasedwith NMP. After drying under about 200 mbar (120° C.) for 16 hours andthen under <10 mbar for 8 hours, a clear coating film was obtained, thisfilm retaining its scratch resistance and flexural strength even afterstorage in boiling water for 4 hours and subsequent storage in acetoneat room temperature for 4 hours.

B. Metal coating from a powder of the polyether aramide

The polymer powder from Example 5 was applied to a sheet of copper whichhad first been cleaned with NMP, and was stoved in a preheated vacuumdrying cabinet under 0.5 mbar at 370° C. in the course of 5 hours. Evenafter boiling with water and subsequent treatment with acetone, theoutstanding adhesive strength and scratch resistance of the coating wasretained.

We claim:
 1. A thermoplastically processable aromatic polyether amide ofthe formula (I) ##STR8## in which the symbols Ar, Ar', Ar₁, Ar₂, R, R',Y, x, y and z have the following meanings:Ar is a divalent, substitutedor unsubstituted, aromatic or heteroaromatic radical or a group

    --Ar*--Q--Ar*--

in which Q is a bond or Q represents an --O--, --C(CH₃)₂ --, --CO--,--S--, --SO-- or --SO₂ -- bridge and Ar* is at least one aromaticradical; the carbonyl groups attached to the Ar radical are onnon-adjacent ring carbon atoms optionally substituted by one or twobranched or unbranched C₁ -C₃ -alkyl or alkoxy radicals, aryl or aryloxyradicals, C₁ -C₆ -perfluoroalkyl or perfluoroalkoxy radicals or byfluorine, chlorine, bromine or iodine atoms, and Ar is one to threedifferent radicals, Ar and Ar' are identical or different andindependent of one another and Ar' is the same as Ar or is an Ar--Z--Argroup, in which Z is a --C(CH₃)₂ -- or --O--Ar*--O--bridge; Ar₁ and Ar₂are identical or different from one another and are in each case asubstituted or unsubstituted para- or meta-arylene radical, Y being a--C(CH₃)₂ --, --CO--, --SO₂ --, --S-- or a --C(CF₃)₂ --bridge, whereina) the sum of the mole fractions x, y and z is one, the sum of x and zis not equal to y, and x can be the value zero, b) the ends of thepolymer chain are blocked completely by monofunctional groups R and R'which do not react further in the polymer, R and R' being independent ofone another and identical or different, and are selected from the groupconsisting of the formulae V, VI, VII and VIII ##STR9## wherein, in thecase of end groups VII and/or VIII, the terminal nitrogen in formula (I)is an imide nitrogen, and wherein E is a hydrogen or a halogen atom, oran organic radical, c) the polyether amide has a number averagemolecular weight M_(n) in the range from 5,000 to 50,000 (M_(n) isabsolute number average), d) the molar ratio q (acid component todiamine component) for preparation of the polyether amides of formula Iis in the range from 0.90 to 0.98 and 1.02 to 1.10, exact stoichiometry(q is 1) of the bifunctional components being excluded, and e) the meltviscosity of the polyether amides at the processing temperature does notexceed 10,000 Pascal.s.
 2. An aromatic polyether amide as claimed inclaim 1, which has a Staudinger index in the range from 0.4 to 1.5 dl/gin N-methyl-pyrrolidone at 25° C.
 3. An aromatic polyether amide asclaimed in claim 1, wherein inorganic impurities in the polymer afterpurification is less than 1000 ppm.
 4. An aromatic polyether amide asclaimed in claim 1, wherein the acid component ##STR10## is derived froman acid selected from the group consisting of furandicarboxylic acid,terephthalic acid and isophthalic acid.
 5. An aromatic polyether amideas claimed in claim 1, in which Ar, Ar', Ar₁, Ar₂ and Y in each case isone to three different radicals.
 6. A process for the preparation of athermoplastically processable aromatic polyether amide as claimed inclaim 1, which comprises reacting in a polycondensation one or moredicarboxylic acid derivatives of the formula (VIII)

    W--CO--Ar--CO--W                                           (VIII)

in which W is a fluorine, chlorine, bromine or iodine atom, or an --OHor OR" group, in which R" is a branched or unbranched aliphatic oraromatic radical with at least one diamine, a chain-blocking agent beingadded after the end of polycondensation in a stoichiometric amount ormore than the stoichiometric amount of diamine.
 7. The process asclaimed in claim 6, wherein a monofunctional, optionally substitutedacid halide or acid anhydride is added as the chain-blocking agent. 8.The process as claimed in claim 6, wherein a monofunctional, amine isadded as the chain-blocking agent.
 9. The process as claimed in claim 6,wherein the chain-blocking agent is added in at least the stoichiometricamount.
 10. An aromatic polyether amide as claimed in claim 1, whereinthe aromatic polyether amide comprises units of furandicarboxylic acid.11. An aromatic polyether amide as claimed in claim 1, wherein in eachcase one to three different radicals of the formula --CO--Ar--CO--,--NH--Ar'--NH-- or --NH--Ar₁ --O--Ar₂ --Y--Ar₂ --O--Ar₁ --NH-- areemployed.
 12. The process as claimed in claim 6, wherein thepolycondensation is carried out in an aprotic polar solvent at atemperature in the range from -20° to +120° C.
 13. The process asclaimed in claim 6, wherein, after conclusion of the reaction, 2 to 40by weight of polycondensate are present in solution.
 14. The process asclaimed in claim 6, wherein the dicarboxylic acid derivatives and thediamines are reacted by a solution process.
 15. The process as claimedin claim 6, wherein the dicarboxylic acid derivatives and the diaminesare reacted by a precipitation process.
 16. The process as claimed inclaim 6, wherein the dicarboxylic acid derivatives and the diamines arereacted by a melt condensation process.
 17. A shaped article of thepolyether amide of claim
 1. 18. An aromatic polyether amide as claimedin claim 11, which contains units selected from the group consisting of2,2-bis 4-(4-aminophenoxy)-phenyl!propane and bis4-(4-aminophenoxy)phenyl!sulfone.
 19. The process as claimed in claim 7,wherein the acid halide or acid anhydride is aromatic.
 20. The processas claimed in claim 8, wherein the amine is aromatic.